Process for producing polymer, the polymer, and curable composition comprising the polymer

ABSTRACT

This invention provides method of producing a polymer which comprises substitution of carboxylic acid group for a terminal halogen group of a polymer obtainable by atom transfer radical polymerization. The carboxylic acid group may be a carboxylic acid salt group, more preferably a carboxylic acid potassium salt group. In carrying out the atom transfer radical polymerization in the practice of the invention, a transition metal complex can be used as a polymerization catalyst. The transition metal complex may be a transition metal complex with an element of the group 7, 8, 9, 10 or 11 of the periodic table as the central atom, more preferably a copper, nickel, ruthenium or iron complex and, in particular, a copper complex is used. The polymer obtainable by atom transfer radical polymerization is obtained by polymerization of a (meth)acrylic monomer, particularly the polymer obtained by polymerization of an acrylic acid ester monomer.

TECHNICAL FIELD

The present invention relates to the reaction of the terminal halogenatom of a vinyl polymer having a specific structure with a carboxylicacid group.

BACKGROUND ART

To produce long-chain polymers by coupling growing terminals of polymersto each other is known in the art. In the case of anion polymerization,such coupling can be effected by adding a compound having twoelectrophilic functional groups. In the case of cation polymerization,the coupling can be effected in the same manner by adding a compoundhaving two nucleophilic functional groups.

On the other hand, it is known that polymers having a terminalfunctional group, either alone or in combination with an appropriatecuring agent, can be crosslinked to give cured products excellent inheat resistance and durability. Among others, hydroxy- or crosslinkablesilyl-terminated polymers are typical examples. Hydroxy-terminatedpolymers can be crosslinked and cured by using a polyfunctionalisocyanate compound as a curing agent. Crosslinkable silyl-terminatedpolymers absorb moisture in the presence of an appropriate condensationcatalyst, to give cured products.

As the main chain skeleton of such hydroxy- or crosslinkablesilyl-terminated polymers, there may be mentioned polyether polymerssuch as polyethylene oxide, polypropylene oxide and polytetramethyleneoxide, hydrocarbon polymers such as polybutadiene, polyisoprene,polychloroprene and polyisobutylene, and hydrogenation products derivedtherefrom, and polyester polymers such as polyethylene terephthalate,polybutylene terephthalate and polycaprolactone, among others. Thesepolymers are used for various purposes according to the main chainskeleton and the mode of crosslinking.

In contrast to the coupling reaction relevant to those polymersobtainable by ionic polymerization or polycondensation, the art ofcoupling together the termini of vinyl polymers obtainable by radicalpolymerization has scarcely been put to practical use. In the case ofradical polymerization as contrasted to ionic polymerization, althoughit is possible theoretically to directly couple together radicals whichare growing termini, because the radical polymerization reaction itselfcannot be easily controlled and, hence, the coupling reaction is hardlycontrollable.

Among vinyl polymers, (meth)acrylic polymers have high weatheringresistance, transparency and other characteristics, which cannot beexpected of the above-mentioned polyether polymers, hydrocarbon polymersor polyester polymers. Among others, (meth)acrylic polymers havingalkenyl or crosslinking silyl groups on side chains are used in highweathering resistance coatings and the like. On the other hand, it isnot easy to control the polymerization of acrylic polymers due to sidereactions and it is very difficult to couple growing termini thereof.

As the advantages of such a crosslinking reaction, there may bementioned the increase in molecular weight as resulting from chainextension and the possibility of synthesizing block copolymers and ofsynthesizing functional group-terminated polymers, among others. Uponcoupling, the molecular weight of a polymer having one growing terminusis doubled and, theoretically, that of a polymer having two growingtermini is indefinitely increased. Upon coupling of a diblock copolymersynthesized by sequential addition of monomers, a triblock copolymer oftype ABA is synthesized. In the case of a polymer as polymerized using afunctional group-containing initiator, coupling of growing termini givesa polymer having the functional groups at both termini.

Vinyl polymers having crosslinking functional groups at both terminigive cured products having superior physical characteristics as comparedwith those having crosslinking functional groups in side chains.Therefore, a number of workers have so far made investigations to findout a simple and easy method of producing the same. However, it is stillnot easy to produce them on an industrial scale. In Japanese KokaiPublication Hei-05-255415, there is disclosed a method of synthesizing(meth)acrylic polymers having alkenyl groups at both termini whichcomprise using an alkenyl-containing disulfide as a chain transferagent. Japanese Kokai Publication Hei-5-262808 discloses a process forsynthesizing a (meth)acrylic polymer having alkenyl groups at bothtermini which comprises synthesizing a (meth)acrylic polymer havinghydroxyl groups at both termini using a hydroxy-containing disulfideand, taking advantage of the reactivity of said hydroxyl group,introducing alkenyl groups at both termini. However, it is not easy tocontrol the molecular weight of the polymer in these methods. Further,for terminally introducing an alkenyl group with certainty, the use of achain transfer agent in a substantial amount is essential, which raisesa problem from production process points of view, however.

Furthermore, since these methods use ordinary radical polymerizationtechniques, it is not easy to control the molecular weight and molecularweight distribution (ratio of number average molecular weight to weightaverage molecular weight) of the polymer to be obtained.

Among functional groups, the carboxyl group can react with variousreactive groups such as hydroxy, amino and epoxide, hence is afunctional group effective as a crosslinking group. The use of afunctional group-containing chain transfer agent as a means forintroducing a carboxyl group into a polymer terminus is known in theart. Japanese Kokai Publication Hei-08-208759 and JP 1603919, forinstance, disclose a technology for synthesizing carboxyl-terminated(meth)acrylic polymers using a mercaptocarboxylic acid as the chaintransfer agent.

Meanwhile, graft copolymers are used as functional materials in variousfields. For synthesizing graft copolymers with vinyl polymers asbranching polymers, some methods are known. Thus, for example, a methodof polymerization is known which comprises causing polymer branches togrow by polymerizing a monomer from polymerization initiation sites on astem polymer (synthetic method 1). Another comprises using a polymer(macromonomer) having a terminal polymerizable double bond as a branchpolymer and synthesizing a stem polymer later by homopolymerizing themacromonomer or copolymerizing the same with another vinyl monomer(synthetic method 2). According to synthetic method 1, radicals areformed on a stem polymer by utilizing a radical generator such asbenzoyl peroxide or by irradiation of radiation and causing thepolymerization of a branch polymer-constituting vinyl monomer toinitiate from those radicals. Though it is simple and easy, syntheticmethod 1 cannot be free from side reactions, such as formation ofhomopolymers of the vinyl monomer used and/or decomposition of the stempolymer. As for synthetic method 2, it has the advantage that a graftcopolymer having a definite structure can be obtained since the branchpolymer is synthesized in advance. However, it is not easy to synthesizemacromonomers, and only limited macromonomer species can be used.

On the other hand, a coupling method which comprises synthesizing afunctional group-terminated branch polymer beforehand and coupling thebranch polymer to a stem polymer utilizing the reactivity of thefunctional group (synthetic method 3) is also known. As the functionalgroup-terminated branch polymer, there may be mentioned, for example,the polymer comprising the main chain skeleton as follows: thus,polyether polymers such as polyethylene oxide, polypropylene oxide andpolytetramethylene oxide, hydrocarbon polymers such as polybutadiene,polyisoprene, polychloroprene, polyisobutylene and hydrogenationproducts derived from these, and polyester polymers such as polyethyleneterephthalate, polybutylene terephthalate and polycaprolactone.

It is an object of the present invention to provide a method of couplingvinyl polymers, a method of terminal functional group introduction, amethod of producing graft polymers, an improved method for carrying outsuch a reaction, and polymers produced by these methods.

DISCLOSURE OF THE INVENTION

The present invention provides a method of producing a polymer

which comprises substitution of carboxylic acid group for the terminalhalogen atom of a polymer obtainable by atom transfer radicalpolymerization.

The carboxylic acid group is preferably a carboxylic acid salt group,more preferably a carboxylic acid potassium salt group.

In carrying out the atom transfer radical polymerization in the practiceof the invention, a transition metal complex can be used as apolymerization catalyst. The transition metal complex is preferably atransition metal complex with an element of the group 7, 8, 9, 10 or 11of the periodic table as the central atom, more preferably a copper,nickel, ruthenium or iron complex and, in particular, a copper complexis preferred.

The polymer obtainable by atom transfer radical polymerization ispreferably the polymer obtained by polymerization of a (meth)acrylicmonomer, particularly the polymer obtained by polymerization of anacrylic acid ester monomer.

The terminal halogen atom of the polymer obtained by atom transferradical polymerization is preferably a secondary halogen atom.

The reaction involved in the production method of the invention can beaccelerated by carrying out it in the presence of a nitrogenatom-containing compound. The nitrogen atom-containing compound ispreferably one selected from the group consisting of aliphatic amines,alicyclic amines, aromatic amines and heterocyclic nitrogen bases.Further, when an amine compound or pyridine compound is used as theligand of a polymerization catalyst in atom transfer radicalpolymerization, it is also effective to use that ligand as the nitrogenatom-containing compound or, when an amine compound or pyridine compoundis used as the ligand of a polymerization catalyst in atom transferradical polymerization, it is also effective, in carrying out thereaction for substituting a carboxylic acid group for the terminalhalogen atom, to add the carboxyl-containing compound directly to thevinyl monomer polymerization system.

The carboxylic acid group-containing compound to be used may be apolymer, or a polymer having carboxylic acid groups on side chains, or acompound having two or more carboxylic acid groups, for instance.

As the polymer obtainable by the reaction according to the invention,there may be mentioned graft polymers, gels, coupled polymers,terminally functional polymers, in particular carboxylic acidgroup-terminated polymers, and so forth.

Also applicable as the carboxylic acid group-containing compound arecompounds obtained by reacting a cyclic acid anhydride with a functionalgroup-containing alcohol and, as the functional group, there may bementioned one selected from the group consisting of alkenyl, hydroxy,amino and epoxy groups. As the cyclic acid anhydride, there may bementioned one selected from the group consisting of succinic anhydride,phthalic anhydride and glutaric anhydride.

The present invention is also directed to the polymer produced by theabove-mentioned production method of the invention.

The vinyl polymer having a carboxyl group at a main chain terminus asobtainable by the production method of the present invention can be usedin curable compositions which contain said polymer as a constituent,together with another component such as an epoxy-containing compound, ahydroxy-containing compound, an amino-containing compound, anisocyanato-containing compound, etc.

BEST MODES FOR CARRYING OUT THE INVENTION

In the following, the halogen-terminated polymer obtainable by atomtransfer radical polymerization (hereinafter referred to as “polymer A”)and the compound having a carboxylic acid group substituting for theterminal halogen atom (hereinafter referred to as “compound B”) aredescribed.

<Description of Polymer A>

In the following, the halogen-terminated polymer A obtainable by atomtransfer radical polymerization is described.

Outline of Atom Transfer Radical Polymerization

The “living radical polymerization” proceeds at a high polymerizationrate and hardly undergoes a termination reaction and gives a polymerwith a narrow molecular weight distribution (an Mw/Mn value of about 1.1to 1.5) in spite of its being a mode of radical polymerization which isgenerally considered to be difficult to control because of the tendencytoward occurrence of a termination reaction such as radical-to-radicalcoupling. It is also possible, in living radical polymerization, toliberally control the molecular weight by adjusting themonomer/initiator charge ratio.

The “living radical polymerization” method thus can give a low viscositypolymer with a narrow molecular weight distribution and, in addition,makes it possible to introduce a specific functional group-containingmonomer into the polymer mostly at the desired sites and, therefore, ispreferred as the method of producing the above specific functionalgroup-containing vinyl polymer.

While the term “living polymerization”, in its narrower sense, meanspolymerization in which molecular chains grow while the termini thereofalways retain their activity, said term generally includes, within themeaning thereof, quasi-living polymerization in which molecular chainsgrow while terminally inactivated molecules and terminally activemolecules are present in a state of equilibrium. The latter definitionapplies to the living polymerization to be employed in the practice ofthe present invention.

The “living radical polymerization” has recently been studied by variousgroups of researchers with great enthusiasm. As examples, there may bementioned, among others, the use of a cobalt-porphyrin complex asdescribed in J. Am. Chem. Soc., 1994, vol. 116, pages 7943 ff, the useof a radical capping agent such as a nitroxide compound as described inMacromolecules, 1994, vol. 27, pages 7228 ff., and the technique of“atom transfer radical polymerization (ATRP)” which uses an organichalide or the like as the initiator and a transition metal complex asthe catalyst.

Among various “living radical polymerization” techniques, the above“atom transfer radical polymerization” technique, which uses an organichalide, a halogenated sulfonyl compound or the like as the initiator anda transition metal complex as the catalyst for polymerizing vinylmonomers, has, in addition to the above-mentioned advantages of “livingradical polymerization”, the advantage that it gives a polymer having ahalogen or the like, which is relatively advantageous for functionalgroup conversion, at main chain termini and that the degree of freedomin initiator and catalyst designing is large and, therefore, is morepreferred as the method for producing vinyl polymers having a specificfunctional groups. This atom transfer radical polymerization isdescribed, for example, by Matyjaszewski et al. in J. Am. Chem. Soc.,1995, vol. 117, pages 5614 ff.; Macromolecules, 1995, vol.28, pages 7901ff.; Science, 1996, vol. 272, pages 866 ff.; WO 96/30421, WO 97/18247,WO 98/01480 and WO98/40415, and by Sawamoto et al. in Macromolecules,1995, vol. 28, pages 1721 ff; Japanese Kokai Publication Hei-09-208616and Japanese Kokai Publication Hei-08-41117, among others.

The atom transfer radical polymerization includes, within the meaningthereof, not only the above-mentioned ordinary atom transfer radicalpolymerization in which an organic halide or halogenated sulfonylcompound is used as the initiator but also the “reverse atom transferradical polymerization” in which a standard free radical polymerizationinitiator, such as a peroxide, is used in combination with ahigher-oxidized-state complex of an ordinary atom transfer radicalpolymerization catalyst, such as a copper (II) complex.

Monomer

The vinyl monomer to be used in the practice of the invention is notparticularly restricted but includes various species. As examples, theremay be mentioned (meth)acrylic acid, methyl(meth)acrylate,ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate,n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate,n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate,n-heptyl(meth)acrylate, n-octyl(meth)acrylate,2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate,dodecyl(meth)acrylate, phenyl(meth)acrylate, toluyl(meth)acrylate,benzyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,3-methoxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, stearyl(meth)acrylate,glycidyl(meth)acrylate, 2-aminoethyl(meth)acrylate,γ-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid-ethyleneoxide adducts, trifluoromethylmethyl(meth)acrylate,2-trifluoromethylethyl(meth)acrylate,2-perfluoroethylethyl(meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,2-perfluoroethyl(meth)acrylate, perfluoromethyl(meth)acrylate,diperfluoromethylmethyl(meth)acrylate,2-perfluoromethyl-2-perfluoroethylmethyl(meth)acrylate,2-perfluorohexylethyl(meth)acrylate,2-perfluorodecylethyl(meth)acrylate,2-perfluorohexadecylethyl(meth)acrylate and like (meth)acrylic monomers;styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonicacid and salts thereof, and like styrenic monomers; perfluoroethylene,perfluoropropylene, vinylidene fluoride and like fluorine-containingvinyl monomers; vinyltrimethoxysilane, vinyltriethoxysilane and likesilicon-containing vinyl monomers; maleic anhydride, maleic acid, maleicacid monoalkyl esters and dialkyl esters; fumaric acid, fumaric acidmonoalkyl esters and dialkyl esters; maleimide, methylmaleimide,ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide,cyclohexylmaleimide and like maleimide monomers; acrylonitrile,methacrylonitrile and like nitrile group-containing vinyl monomers;acrylamide, methacrylamide and like amide group-containing vinylmonomers; vinyl acetate, vinyl propionate, vinyl pivalate, vinylbenzoate, vinyl cinnamate and like vinyl esters; ethylene, propylene andlike alkenes; butadiene, isoprene and like conjugated dienes; vinylchloride, vinylidene chloride, allyl chloride and allyl alcohol, amongothers. These may be used singly or a plurality of such monomers may becopolymerized. Among them, styrenic monomers and (meth)acrylic monomersare preferred from the viewpoint of physical properties of products,among others. Acrylic ester monomers and methacrylic ester monomers aremore preferred and butyl acrylate is still more preferred. In thepractice of the invention, these preferred monomers may be copolymerizedwith some other monomer and, in that case, the proportion of thepreferred monomers is preferably not less than 40% by weight.

Initiator

In the atom transfer radical polymerization, an organic halide (e.g. anester compound having a halogen atom at the α position or a compoundhaving a halogen atom at the benzyl position) or a halogenated sulfonylcompound is generally used as the initiator. A substituent capable ofserving as a substitute for a halogen atom may also be used. Specificexamples are, among others:

C₆H₅—CH₂X,

C₆H₅—C(H)(X)CH₃,

C₆H₅—C(X)(CH₃)₂,

(in the above chemical formulas, C₆H₅ is a phenyl group and X ischlorine, bromine or iodine);

R¹—C(H)(X)—CO₂R²,

R¹—C(CH₃)(X)—CO₂R²,

R¹—C(H)(X)—C(O)R²,

R¹—C(CH₃)(X)—C(O)R²,

(in which R¹ and R²are the same or different and each is a hydrogen atomor an alkyl group containing 1 to 20 carbon atoms, an aryl groupcontaining 6 to 20 carbon atoms or an aralkyl group containing 7 to 20carbon atoms and X is chlorine, bromine or iodine); and

R¹—C₆H₄—SO₂X,

(in which R¹, R² and X are as defined above).

It is also possible to use, as the initiator in living radicalpolymerization an organic halide or halogenated sulfonyl compound havinga functional group other than the functional group for initiating thepolymerization. In such a case, vinyl polymers having the functionalgroup at one main chain terminus and the halogen atom at the other mainchain terminus are produced. As such functional group, there may bementioned alkenyl, crosslinking silyl, hydroxy, epoxy, amino and amidegroups, among others.

The alkenyl-containing organic halide is not particularly restricted butmay be one having the structure shown under the general formula (1):

R⁴R⁵C(X)—R⁶—R⁷—C(R³)═CH₂  (1)

wherein R³ is a hydrogen atom or a methyl group, R⁴ and R⁵ are the sameor different and each is a hydrogen atom or an monovalent alkyl, aryl oraralkyl group containing up to 20 carbon atoms and R⁴ and R⁵ may bebound to each other at respective other termini, R⁶ is —C(O)O— (estergroup), —C(O)— (keto group) or an o-, m- or p-phenylene group, R⁷ is adirect bond or a divalent organic group containing 1 to 20 carbon atoms,which may optionally contain one or more ether bonds, and X is chlorine,bromine or iodine.

As specific examples of the substituents R⁴ and R⁵, there maybementioned hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl,hexyl, etc. R⁴ and R⁵ may be bound to each other at respective othertermini to form a cyclic skeleton.

As specific examples of the alkenyl-containing organic halide shownunder the general formula (1), there may be mentioned the following:

XCH₂C(O)O(CH₂)_(n)CH═CH₂,

H₃CC(H)(X)C(O)O(CH₂)_(n)CH═CH₂,

(H₃C)₂C(X)C(O)O(CH₂)_(n)CH═CH₂,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)CH═CH₂

(in the above formulas, X is chlorine, bromine or iodine and n is aninteger of 0 to 20);

XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

 (H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,

(in the above formulas, X is chlorine, bromine or iodine, n is aninteger of 1 to 20 and m is an integer of 0 to 20);

o, m, p-XCH₂—C₆H₄—(CH₂)_(n)—CH═CH₂,

o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,

(in the above formulas, X is chlorine, bromine or iodine and n is aninteger of 1 to 20);

o, m, p-XCH₂—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂

o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂

(in the above formulas, X is chlorine, bromine or iodine, n is aninteger of 1 to 20 and m is an integer of 0 to 20);

o, m, p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂

o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂

(in the above formulas, X is chlorine, bromine or iodine and n is aninteger of 1 to 20);

o, m, p-XCH₂—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂

o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂

(in the above formulas, X is chlorine, bromine or iodine, n is aninteger of 1 to 20 and m is an integer of 0 to 20).

As the alkenyl-containing organic halide, there may further be mentionedcompounds represented by the general formula (2):

H₂C═C(R³)—R⁶—C(R⁴)(X)—R⁸—R⁵  (2)

wherein R³, R⁴, R⁵, R⁶ and X are as defined above and R⁸ is a directbond, —C(O)O— (ester group), —C(O)— (keto group) or an o-, m- orp-phenylene group.

R⁶ is a direct bond or a divalent organic group containing 1 to 20carbon atoms (which may optionally contain one or more ether bonds) and,when it is a direct bond, the vinyl group is bound to the carbon towhich the halogen is bound, to form an allyl halide. In this case, thecarbon-halogen bond is activated by the neighboring vinyl group, so thatit is not always necessary for R⁸ to be a C(O)O group or a phenylenegroup, for instance, but it may be a direct bond. When R⁶ is not adirect bond, for activating the carbon-halogen bond, R⁸ is preferably aC(O)O group, C(O) group or phenylene group.

Specific examples of the compound of the general formula (2) are, amongothers, the following:

CH₂═CHCH₂X, CH₂═C(CH₃)CH₂X, CH₂═CHC(H)(X)CH₃,

CH₂═C(CH₃)C(H)(X)CH₃, CH₂═CHC(X)(CH₃)₂,

CH₂═CHC(H)(X)C₂H₅, CH₂═CHC(H)(X)CH(CH₃)₂,

CH₂═CHC(H)(X)C₆H₅, CH₂═CHC(H)(X)CH₂C₆H₅,

CH₂═CHCH₂C(H)(X)—CO₂R, CH₂═CH(CH₂)₂C(H)(X)—CO₂R,

CH₂═CH(CH₂)₃C(H)(X)—CO₂R, CH₂═CH(CH₂)₈C(H)(X)—CO₂R,

CH₂═CHCH₂C(H)(X)—C₆H₅, CH₂═CH(CH₂)₂C(H)(X)—C₆H₅,

CH₂═CH(CH₂)₃C(H)(X)—C₆H₅,

(in the above formulas, X is chlorine, bromine or iodine and R is analkyl group, aryl group or aralkyl group containing up to 20 carbonatoms).

Specific examples of the alkenyl-containing halogenated sulfonylcompound are as follows:

o, m, p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X,

o, m, p-CH₂═CH—(CH₂)_(n)—O—C₆H₄—SO₂X,

wherein, in each formula, X is chlorine, bromine or iodine and n is aninteger of 0 to 20, and the like.

The above-mentioned crosslinking silyl-containing organic halide is notparticularly restricted but includes, among others, those having astructure shown by the general formula (3):

R⁴R⁵C(X)—R⁶—R⁷—C(H)(R³)CH₂—[Si(R⁹)_(2−b)(Y)_(b)O]_(m)—Si(R¹⁰)_(3−a)(Y)_(a)  (3)

wherein R³, R⁴, R⁵, R⁶, R⁷ and X are as defined above, R⁹ and R¹⁰ eachrepresents an alkyl, aryl or aralkyl group containing up to 20 carbonatoms or a triorganosiloxy group of the formula (R′)₃SiO— (in which R′is a monovalent hydrocarbon group containing 1 to 20 carbon atoms, andthe three R′ groups may be the same or different) and, when there aretwo or more R⁹ or R¹⁰ groups, they may be the same or different, Yrepresents a hydroxy group or a hydrolyzable group and, when there aretwo or more Y groups, they may be the same or different, a represents 0,1, 2 or 3, b represents 0, 1 or 2 and m is an integer of 0 to 19,provided that the relation a +mb≧1 should be satisfied. Specificexamples of the compound of the general formula (3) are as follows:

XCH₂C(O)O(CH₂)_(n)Si(OCH₃)₃,

CH₃C(H)(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,

(CH₃)₂C(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,

XCH₂C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,

CH₃C(H)(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,

(CH₃)₂C(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,

(in the above formulas, X is chlorine, bromine or iodine and n is aninteger of 0 to 20);

XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,

XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,

H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,

(H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,

CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,

(in the above formulas, X is chlorine, bromine or iodine, n is aninteger of 1 to 20 and m is an integer of 0 to 20);

o, m, p-XCH₂—C₆H₄—(CH₂)₂Si(OCH₃)₃,

o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,

 o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,

o, m, p-XCH₂—C₆H₄—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,

o, m, p-XCH₂—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-XCH₂—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-XCH₂—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,

(in the above formulas, X is chlorine, bromine or iodine), and the like.

As further examples of the crosslinking silyl-containing organic halide,there may be mentioned those having a structure represented by thegeneral formula (4):

(R¹⁰)_(3−a)(Y)_(a)Si—[OSi(R⁹)_(2−b)(Y)_(b)]_(m)—CH₂—C(H)(R³)—R¹¹—C(R⁴)(X)—R⁸—R⁵  (4)

wherein R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, a, b, m, X and Y are as definedabove.

Specific examples of such compounds are as follows:

(CH₃O)₃SiCH₂CH₂C(H)(X)C₆H₅,

(CH₃O)₂(CH₃)SiCH₂CH₂C(H)(X)C₆H₅,

(CH₃O)₃Si(CH₂)₂C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₂C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₃C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₄C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₉C(H)(X)—CO₂R,

(CH₃O)₂(CH₃)Si(CH₂)₉C(H)(X)—CO₂R,

(CH₃O)₃Si(CH₂)₃C(H)(X)—C₆H₅,

(CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—C₆H₅,

 (CH₃O)₃Si(CH₂)₄C(H)(X)—C₆H₅,

(CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—C₆H₅,

(in the above formulas, X is chlorine, bromine or iodine and R is analkyl, aryl or aralkyl group containing up to 20 carbon atoms), and thelike.

The above-mentioned hydroxy-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, amongothers, compounds of the formula:

HO—(CH₂)_(n)—OC(O)C(H)(R)(X)

wherein X is chlorine, bromine or iodine, R is a hydrogen atom or analkyl, aryl or aralkyl group containing up to 20 carbon atoms and n isan integer of 1 to 20.

The above-mentioned amino-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, amongothers, compounds of the formula:

H₂N—(CH₂)_(n)—OC(O)C(H)(R)(X)

wherein X is chlorine, bromine or iodine, R is a hydrogen atom or analkyl, aryl or aralkyl group containing up to 20 carbon atoms and n isan integer of 1 to 20.

The above-mentioned epoxy-containing organic halide or halogenatedsulfonyl compound is not particularly restricted but includes, amongothers, compounds of the formula:

wherein X is chlorine, bromine or iodine, R is a hydrogen atom or analkyl, aryl or aralkyl group containing up to 20 carbon atoms and n isan integer of 1 to 20.

When the above living radical polymerization is carried out using anorganic halide or halogenated sulfonyl compound having two or moreinitiation sites as the initiator, vinyl polymers having halogen atomsat both termini are obtained. Specific examples of such initiator are:

(in which R represents an alkyl group containing 1 to 20 carbon atoms,an aryl group containing 6 to 20 carbon atoms or an aralkyl groupcontaining 7 to 20 atoms, C₆H₄ represents a phenylene group, nrepresents an integer of 0 to 20 and X represents chlorine, bromine oriodine atom.);

(in which R represents an alkyl group containing 1 to 20 carbon atoms,an aryl group containing 6 to 20 carbon atoms or an aralkyl groupcontaining 7 to 20 atoms, C₆H₄ represents a phenylene group, nrepresents an integer of 0 to 20 and X represents chlorine, bromine oriodine); and so on.

Catalyst

The transition metal complex to be used as a catalyst in the atomtransfer radical polymerization is not particularly restricted but thosedescribed in PCT/US 96/17780 can be utilized. Preferred among them arezero-valent copper, monovalent copper, divalent ruthenium, divalent ironand divalent nickel complexes. In particular, copper complexes arepreferred. Specific examples of the monovalent copper compound arecuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide,cuprous oxide, cuprous perchlorate and the like. Thetristriphenylphosphine complex of divalent ruthenium chloride(RuCl₂(PPh₃)₃) is also suited for use as the catalyst. When a rutheniumcompound is used as the catalyst, an aluminum alkoxide is added as anactivator. Further, bistriphenylphosphine-divalent iron complex(FeCl₂(PPh₃)₂), bistriphenylphosphine-divalent nickel complex(NiCl₂(PPh₃)₂) and bistributylphosphine-divalent nickel (NiBr₂(PBu₃)₂)complex are also suited as the catalysts.

When a copper compound is used as the catalyst, those ligands describedin PCT/US 96/17780 can be used as the ligands for the copper compound.Amine ligands are preferred although the ligands are not particularlyrestricted. Thus, preferred ligands are 2,2′-bipyridyl and derivativesthereof, 1,10-phenanthroline and derivatives thereof, and aliphaticamines such as trialkylamines, tetramethylethylenediamine,pentamethyldiethylenetriamine and hexamethyl(2-aminoethyl)amine, and thelike. Among them, aliphatic polyamines such aspentamethyldiethylenetriamine and hexamethyl(2-aminoethyl)amine arepreferably used in the practice of the present invention.

Since the terminal halogen atom disappearance is influenced by thebasicity of the polymerization system in the polymerization carried outunder dehydrated conditions in the practice of the invention, theeffects of the invention are great when amines, in particular aliphaticamines, are used as ligands.

The catalyst may be added to the polymerization apparatus in the form ofa complex having catalyst activity or a transition metal compound, whichis a precursor of the catalyst, and a ligand may be admixed in thepolymerization apparatus for complex formation. According to the knownatom transfer radical polymerization techniques, this complex formationprocedure is carried out prior to addition of the initiator. On thecontrary, the present invention discloses the technique which comprisesadding the ligand to the polymerization system after addition of theinitiator to effect complex formation with the catalyst precursortransition metal compound and thereby cause development of the catalyticactivity and initiate the polymerization and/or control the catalyticactivity.

When the polymerization is carried out in the presence of a nitrilecompound in the practice of the present invention, it is preferred that,even in the ordinary technique for initiating atom transfer radicalpolymerization which comprises adding an initiator after complexformation, the complex precursor transition metal compound and nitrilecompound be mixed together prior to ligand addition, since thedispersibility of the complex is increased by doing so.

Under the ordinary atom transfer radical polymerization conditions, theaddition amount of such a ligand as mentioned above is determined by thenumber of coordination sites of the transition metal and the totalnumber of coordinating groups of the ligand molecule or molecules andcontrolled in a manner such that both numbers are almost the same. Thus,for example, 2,2′-bipyridyl and derivatives thereof are added generallyin an amount of two moles per mole of CuBr, and in the case ofpentamethyldiethylenetriamine, the addition amount is one mole on thesame basis. When the polymerization is initiated and/or the catalyticactivity is controlled by ligand addition in the practice of theinvention, it is preferred that the metal atom be in excess of theligand, although this is not an essential requirement. The ratio betweenthe coordination number and the number of ligand groups is preferablynot less than 1.2, more preferably not less than 1.4, most preferablynot less than 1.6, in particular not less than 2.

In the practice of the invention, the use of a transition metal complexin which the ligand is a nitrile compound from the beginning in lieu ofthe addition of a nitrile compound also gives the same effects. As sucha complex, which is not particularly restricted, there may be mentionedthose which are obtainable by adding a transition metal compound to asystem in which a ligand nitrile compound occurs in excess and thenremoving the excess nitrile compound. CuBr(NC—R)_(n) and CuCl(NC—R)_(n)(R being a monovalent organic group, such as methyl, and n being aninteger of not less than 1) are also examples.

Solvent, Additive

The polymerization according to the invention can be carried withoutusing any solvent or in various solvents. The above solvents include,among others, hydrocarbon solvents such as benzene and toluene; ethersolvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisoleand dimethoxybenzene; halogenated hydrocarbon solvents such as methylenechloride, chloroform and chlorobenzene; ketone solvents such as acetone,methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such asmethanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butylalcohol; nitrile solvents such as acetonitrile, propionitrile andbenzonitrile; ester solvents such as ethyl acetate and butyl acetate;and carbonate solvents such as ethylene carbonate and propylenecarbonate. These may be used singly or two or more of them may be usedin admixture.

Among these solvents, aprotic solvents are preferred. Further, highlypolar solvents are generally high in water absorbing ability and tend toaccelerate the terminal group disappearance reaction and therefore aremore effective in the polymerization under dehydrating conditionsaccording to the invention. As a criterion, there may be mentioned thecase in which a solvent having a relative dielectric constant at 25° C.of not less than 10 is used. Those nitrile compounds which are mentionedherein for use as additives in the practice of the invention may also beused as solvents.

It is preferred that these solvents or other additives to be added tothe polymerization system coordinate with a metal compound used as thecatalyst and form complexes having no catalytic activity but, uponaddition of a ligand, the complexes are converted to active catalysts.Even when the solvent employed has no coordinating ability, thecatalytic activity can be controlled by addition of a ligand. In aligand-free state, however, such a metal compound as CuBr isinsufficient in dispersibility and, in some instances, it adheres to thevessel wall, for instance and makes it difficult to stably control theactivity. An example in which such requirements as mentioned above aresatisfied is the combination of CuBr as the metal compound and a nitrilesolvent as the solvent. In PCT/US 96/17780, acetonitrile is described asa preferred ligand to the polymerization catalyst but, in fact, it hasbeen confirmed that the acetonitrile complex of CuBr has nopolymerization activity. Studies made by the present inventors, however,have revealed that this complex has high crystallinity and can be welldispersed in the polymerization system by adequate stirring though inheterogeneously. And, when such a ligand aspentamethyldiethylenetriamine is added, an active complex are quicklyformed to thereby catalyze the polymerization.

Molecular Weight and Molecular Weight Distribution

Since it is produced under better control by atom transfer radicalpolymerization, the polymer A generally has a molecular weightdistribution, namely the ratio of weight average molecular weight tonumber average molecular weight as determined by gel permeationchromatography, of less than 1.8, preferably not more than 1.7, morepreferably not more than 1.6, still more preferably not more than 1.5,in particular not more than 1.4 and most preferably not more than 1.3,although these values have no restrictive meaning. In the practice ofthe invention, the GPC determination is generally carried out on apolystyrene gel column using chloroform as the mobile phase, and thenumber average molecular weight can be determined in terms ofpolystyrene equivalent. Though it is not particularly restricted, thenumber average molecular weight is preferably within the range of 500 to1,000,000, more preferably 1,000 to 100,000.

Terminal Halogen-containing Group

The terminal halogen-containing group of polymer A has a structurerepresented, for example, by the following general formula:

—C(R⁵¹)(R⁵²)(X)

wherein R⁵¹ and R⁵² each represents a group bound to an ethylenicallyunsaturated bond of a vinyl monomer and X represents chlorine, bromineor iodine.

The case in which either of R⁵¹ and R⁵² is a hydrogen atom, namely asecondary halogen group, is preferred among others. For realizing this,mention may be made of the polymerization of such a monomer as anacrylic monomer and, further, of the technique of adding a monomergiving such a terminal structure only at the terminal stage ofpolymerization and cause it to polymerize.

<Description of Compound B Having a Carboxylic Acid Group>

In the following, the compound B having a carboxylic acid group, whichis to substitute for the terminal halogen atom of the halogen-terminatedpolymer A obtained by atom transfer radical polymerization is described.

The carboxylic acid group-containing compound includes a polymers,polymers further having carboxylic acid groups in side chains thereof,and carboxylic acid-containing compounds having two or more carboxylicacid groups, for instance.

As the carboxylic acid group-containing compound, there may be mentionedreaction products from a cyclic acid anhydride and an functionalgroup-containing alcohol and, as the functional group, there may bementioned a group selected from the group consisting of alkenyl,hydroxy, amino and epoxy groups. The cyclic acid anhydride may beselected from the group consisting of succinic anhydride, phthalicanhydride and glutaric anhydride.

Carboxylic Acid Group

The carboxylic acid group includes carboxylic acids and carboxylic acidsalts, with carboxylic acid salts being preferred.

The carboxylic acid salts are represented by the following generalformula:

—C(O)—O⁻M⁺

wherein M⁺ represents an alkali metal ion or a quaternary ammonium ion.

M⁺ is the counter ion of the carboxylic acid salt and, as species of M⁺,there may be mentioned alkali metal ions, specifically the lithium ion,sodium ion and potassium ion, and quaternary ammonium ions. As thequaternary ammonium ions, there may be mentioned the tetramethylammoniumion, tetraethylammonium ion, trimethylbenzylammonium ion,trimethyldodecylammonium ion, tetrabutylammonium ion anddimethylpiperidinium ion, among others. Among these, the sodium ion andpotassium ion are preferred and the potassium ion is more preferred,without any restrictive meaning, however.

The carboxylic acid group is used as the precursor of the carboxylicacid salt group.

The carboxylic acid salt group can be prepared by reacting thecarboxylic acid group with a base. The base may be any of various bases.Examples are metal alkoxides such as sodium methoxide, potassiummethoxide, lithium methoxide, sodium ethoxide, potassium ethoxide,lithium ethoxide, sodium tert-butoxide and potassium tert-butoxide;carbonate salts such as sodium carbonate, potassium carbonate, lithiumcarbonate and sodium hydrogen carbonate; hydroxides such as sodiumhydroxide and potassium hydroxide; hydrides such as sodium hydride andpotassium hydride; organolithium compounds such as methyllithium,ethyllithium, n-butyllithium, tert-butyllithium, lithiumdiisopropylamide and lithium hexamethyldisilazide; amines such asammonium, trimethylamine, triethylamine, tributylamine,tetramethylethylenediamine and pentamethyldiethylenetriamine; pyridinecompounds such as pyridine and picoline; and the like.

As the solvent to be used in the neutralization of the above precursorcompound with a base, there may be mentioned, among others, hydrocarbonsolvents such as benzene and toluene; halogenated hydrocarbon solventssuch as methylene chloride, chloroform and chlorobenzene; ether solventssuch as diethyl ether, dioxane, tetrahydrofuran, diphenyl ether, anisoleand dimethoxybenzene; ester solvents such as ethyl acetate and butylacetate; ketone solvents such as acetone, methyl ethyl ketone and methylisobutyl ketone; alcohol solvents such as methanol, ethanol, propanol,isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solventssuch as acetonitrile, propionitrile and benzonitrile; amide solventssuch as dimethylfomamide, dimethylacetamide and hexamethylphosphorictriamide; sulfoxide solvents such as dimethyl sulfoxide; carbonatesolvents such as ethylene carbonate and propylene carbonate; and water.These may be used singly or two or more of them may be used inadmixture.

Those salts in which M+ is a quaternary ammonium ion can be obtained bydirectly reacting the carboxylic acid group with an alkylamine orpyridine compound or by preparing a salt in which M⁺ is an alkali metalion and thereafter reacting the resulting salt with a quaternaryammonium halide. As the quaternary ammonium halide, there may bementioned, for example, tetramethylammonium halides, tetraethylammoniumhalides, trimethylbenzylammonium halides, trimethyldodecylammoniumhalides and tetrabutylammonium halides.

Carboxylic Acid Group-containing Polymer

As the carboxylic acid group-containing polymer, there may be mentionedpolymers and polymers further having carboxylic acid groups in sidechains thereof.

The polymers further having a carboxylic acid group in a side chainthereof can be prepared by reacting a vinyl polymer having a carboxylgroup or acid anhydride structure with a base. As such vinyl polymer,there may be mentioned, among others, polymers of a vinyl monomer havinga carboxyl group or acid anhydride structure, such as (meth)acrylicacid; maleic anhydride, maleic acid or a maleic acid monoalkyl ester;fumaric acid or a fumaric acid monoalkyl ester; or cinnamic acid, andvinyl copolymers comprising one or more of these vinyl monomers as oneof the constituent units thereof.

As the carboxylic acid-terminated polymer, there may be mentioned, amongothers, polyesters, and polymers derived by deprotection from polymersobtained by atom transfer radical polymerization using an initiatorhaving a carboxylic acid group protected with a protective group such asa tert-butyl and silyl group.

Compound Having a Plurality of Carboxylic Acid Groups

As the carboxylic acid-containing compound having a plurality ofcarboxylic acid groups, there may be mentioned carboxylic acid saltsrepresented by the following general formula:

R³⁰—[C(O)—O—M⁺]_(n)

wherein R³⁰ represents a direct bond or an organic group containing 1 to20 carbon atoms with a valence n, which may contain one or more etherand/or ester bonds, and M⁺ represents an alkali metal ion or aquaternary ammonium ion.

In the above general formula, R³⁰ is a direct bond or an organic groupcontaining 1 to 20 carbon atoms with a valence n, which may contain oneor more ether and/or ester bonds. Further, R³⁰ may contain anunsaturated double bond or a benzene ring. R³⁰ may be substituted by afunctional group such as hydroxy, amino, nitro, cyano, etc. As specificexamples, there may be mentioned a direct bond; —CH₂—, —CH(CH₃)—,—C(CH₃)₂—, —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)_(n)— (n being an integerof 5 to 20); —CH₂—CH(OH)—, —CH(OH)—CH(OH)—, —CH═CH— and like divalentorganic groups. The following polyvalent organic groups may further bementioned as specific examples:

As the precursor of a carboxylic acid salts of the above generalformula, a polycarboxylic acid having two or more carboxyl groups permolecule may be used. Specific examples are oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, HO₂C—(CH₂)_(n)—CO₂H (n beingan integer of 5 to 20), maleic acid, fumaric acid, malic acid, tartaricacid, citric acid and the like. Further, the polycarboxylic acids shownbelow can be used.

Further usable as the above precursor are acid anhydrides and halides ofthe above-mentioned polycarboxylic acids.

Functional Group-containing Carboxylic Acid Salt Compound

The functional group-containing carboxylic acid salt compound is notparticularly restricted but includes compounds represented by thefollowing general formula which have a functional group Y:

M⁺O⁻—C(O)—R⁴⁰—Y¹

wherein R⁴⁰ represents a direct bond or a divalent organic groupcontaining 1 to 20 carbon atoms, which may optionally contain one ormore ether and/or ester bonds, Y¹ represents a hydroxy group (—OH), anamino group (—NH₂), a carboxyl group (—CO₂H), carboxylate group (—CO₂M⁺)or an alkenyl group represented by —C(R)═CH₂ (where R represents ahydrogen atom or an alkyl group containing 1 to 10 carbon atoms, an arylgroup containing 6 to 10 carbon atoms or an aralkyl group containing 7to 10 carbon atoms) and M⁺ represents an alkali metal ion or aquaternary ammonium ion.

R⁴⁰ is specifically a direct bond or a divalent organic group containing1 to 20 carbon atoms, which may optionally contain one or more etherbond. Specific examples of the divalent organic group containing 1 to 20carbon atoms are —CH₂—, —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)_(n)— (nbeing an integer of 5 to 20) and like alkylene groups. R⁴¹ may containan unsaturated double bond or a benzene ring. Further, R⁴¹ may containan ether, ester or amide bond.

M⁺ is as mentioned above.

Carboxylic acids having a functional group Y¹² are used as the precursorof the carboxylic acid salts represented by the above general formula.Y¹² is a hydroxy group (—OH), an amino group (—NH₂), a carboxyl group(—CO₂H) or an alkenyl group represented by —C(R)—CH₂ (where R representsa hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, anaryl group containing 6 to 10 carbon atoms or an aralkyl groupcontaining 7 to 10 carbon atoms).

The hydroxy-containing carboxylic acid compound is not particularlyrestricted but, for example, the compounds shown below are used:HO—(CH₂)_(n)—CO₂H (n being an integer of 1 to 20), H₃C—CH(OH)—CO₂H,H₃C—CH(OH)CH₂—CO₂H, o-, m- or p-HO—C₆H₄—CO₂H, and o-, m- orp-HO—(CH₂)_(n)—C₆H₄—(CH₂)_(m)—CO₂H (n and m each being an integer of 0to 14 and n+m≦14).

The amino-containing carboxylic acid compound is not particularlyrestricted but amino acids known in the art may be used. Specificexamples are: H₂N—(CH₂)_(n)—CO₂H (n being an integer of 1 to 20),H₃C—CH(NH₂)—CO₂H, H₃C—CH(NH₂)CH₂—CO₂H, C₆H₅—CH(NH₂)—CO₂H and the like.

The alkenyl-containing carboxylic acid compound is not particularlyrestricted but, for example, the following compounds may be used. Asspecific examples, there may be mentioned H₂C═CH—C(O)—OH,H₂C═C(CH₃)—C(O)—OH, H₂C═CH—CH₂—C(O)—OH, H₂C═CH—(CH₂)_(n)—C(O)—OH (nbeing an integer of 0 to 20), H₂C═CH—(CH₂)_(n)—OC(O)—(CH₂)_(m)—C(O)—OH(m and n being the same or different and each being an integer of 0 to19), o-, m- or p-H₂C═CH—C₆H₄—C(O)—OH, o-, m- orp-H₂C═CH—CH₂—C₆H₄—C(O)—OH, o-, m- or p-H₂C═CH—CH₂—O—C₆H₄—C(O)—OH, o-, m-or p-H₂C═CH—(CH₂)_(n)—OC(O)—C₆H₄—C(O)—OH (n being an integer of 0 to 13)and the like.

The carboxyl or carboxylate group-containing precursor of the carboxylicacid salt compound is not particularly restricted but, for example,divalent carboxylic acid compounds and the like are used. As specificexamples, there may be mentioned oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, HO₂C—(CH₂)_(n)—CO₂H (n being aninteger of 5 to 20), maleic acid, fumaric acid, malic acid, tartaricacid, phthalic acid, isophthalic acid, terephthalic acid andnaphthalenedicarboxylic acid. Halides of these and cyclic acidanhydrides such as succinic anhydride, maleic anhydride and phthalicanhydride may also be used.

Carboxylic Acid Group-containing Compound Obtainable by Reacting aCyclic Acid Anhydride with a Functional Group-containing Alcohol

By reacting a cyclic acid anhydride with a functional group-containingalcohol, the anhydride readily undergoes ring opening to give thecorresponding precursor carboxylic acid compound. The cyclic acidanhydride is not particularly restricted but, for example, succinicanhydride, glutaric anhydride, maleic anhydride, cyclohexanedicarboxylicanhydride, phthalic anhydride and the like may be mentioned. Amongthese, succinic anhydride, glutaric anhydride and phthalic anhydride arepreferred and phthalic anhydride is particularly preferred.

The functional group-containing alcohol mentioned above is notparticularly restricted but may be a compound represented by thefollowing general formula:

HO—R—Z

wherein R represents a divalent organic group containing 1 to 20 carbonatoms and Z represents a functional group.

The functional group Z is not particularly restricted but, for example,is an alkenyl group [—C(R′)═CH₂; R′ being hydrogen or methyl], hydroxy,amino, epoxy or the like. As specific examples of the functionalgroup-containing alcohol, there may be mentioned, among others,alkenyl-containing alcohols such as allyl alcohol, butenyl alcohol,pentenyl alcohol and hexenyl alcohol; diols such as ethylene glycol,propylene glycol and cyclohexanediol; amino-containing alcohols such asethanolamine, aminopropanol and aminobutanol; and epoxy-containingalcohols such as glycidol, among others.

When an amino- or hydroxy-containing compound is reacted with a polymerterminus, the compound as it is may be subjected to the reaction but, incase such group may influence on the polymer terminus, the compoundhaving a protective group may be used. As the protective group, theremaybe mentioned acetyl, silyl, alkoxy and like groups.

By reacting the above carboxylic acid compound with a base, it ispossible to obtain an alkali metal salt or ammonium salt.

The method of preparing the alkali metal salt is as already mentionedhereinabove.

<Quantity Ratio Between the Carboxylic Acid Salt Group and Halogen Atom(Coupling)>

In carrying out the coupling reaction, the carboxylic acid salt is usedpreferably in an amount such that the amount of the carboxylic acid saltgroup be not more than equivalent to the amount of the terminal halogenatom. When the carboxylic acid salt is used in an amount in excess ofthe equivalent amount, the mutual coupling reaction between polymertermini may not proceed to a sufficient extent but may give acarboxylate-terminated polymer in some instances. In cases where acarboxylate-terminated polymer is to be obtained, the use in excess ofthe equivalent amount is appropriate. If not, however, the use in excessof the equivalent amount is to be avoided. When the above amount issmaller, there may remain polymer termini that have failed to couple butthis produces no problem if it is intended to effect only partialcoupling. Accordingly, the carboxylic acid salt represented by the abovegeneral formula (3) is preferably used in an amount of 0.5 to 1.0 time,more preferably 0.8 to 1.0 time, still more preferably 0.9 to 1.0 time,as expressed in terms of the carboxylate group amount relative to theterminal halogen. In cases where the compound having a plurality ofcarboxylic acid salt groups is low in solubility, the solubility thereofmay increase as a result of binding thereof with the polymer afterreaction of the first carboxylic acid salt group, hence the reactivityof the second and further groups may increase in certain cases. In suchcases, the use of the carboxylic acid salt in an amount in excess of theequivalent amount also can allow the coupling reaction to proceedsatisfactorily.

<Quantity Ratio Between the Carboxylic Acid Salt Group and Halogen Group(Grafting)>

The polymer B is used preferably in an amount such that the amount ofthe carboxylate group of polymer B is not less than the equivalentamount relative to the amount of the halogen group of polymer A. This isbecause, when the amount is less than the equivalent amount, the polymerA partially remains unreacted. On the other hand, it is possible toretain the unreacted portion of the carboxylate group as a hydrophilicgroup in the copolymer by causing the amount of the carboxylate group tobe in excess of the amount of the halogen group. Thus, it is possible tosynthesize amphophilic polymers by adjusting the quantity ratio betweenthe carboxylate group and halogen group.

<Reaction Conditions>

The solvent to be used in the conversion reaction of the terminalhalogen atom of polymer A includes, among others, hydrocarbon solventssuch as benzene and toluene; halogenated hydrocarbon solvents such asmethylene chloride, chloroform and chlorobenzene; ether solvents such asdiethyl ether, dioxane, tetrahydrofuran, diphenyl ether, anisole anddimethoxybenzene; ester solvents such as ethyl acetate and butylacetate;ketone solvents such as acetone, methyl ethyl ketone and methyl isobutylketone; alcohol solvents such as methanol, ethanol, propanol,isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solventssuch as acetonitrile, propionitrile and benzonitrile; amide solventssuch as dimethylfomamide, dimethylacetamide and hexamethylphosphorictriamide; sulfoxide solvents such as dimethyl sulfoxide; carbonatesolvents such as ethylene carbonate and propylene carbonate; and water.These may be used singly or two or more of them may be used inadmixture. The reaction temperature is not particularly restricted butpreferably is 0° C. to 150° C.

<Reaction in the Presence of a Nitrogen Atom-containing Compound>

Carboxylic acid salts are generally low in solubility in common organicsolvents and, depending on the solvent, produce a problem, namely thesubstitution reaction of a polymer terminus will not proceed at all orproceeds only very slowly. As a result of intensive studies made by thepresent inventors in search of means of solving this problem, it wasfound that this reaction can be accelerated by causing a nitrogenatom-containing compound to coexist in the reaction system.

The nitrogen atom-containing compound is not particularly restricted butmention may be made of ammonia; aliphatic amines such as trimethylamine,triethylamine, tripropylamine, tributylamine, diisopropylethylamine,tetramethylethylenediamine and pentamethyldiethylenetriamine; alicyclicamines such as dimethylcyclohexylamine, diethylcyclohexylamine andmethyldicyclohexylamine; aromatic amines such as dimethylaniline anddiethylaniline; and heterocyclic nitrogen bases such as methylpyrazole,phenylpyrazole, methylimidazole, phenylimidazole, pyridine and picoline,among others. These maybe used singly or two or more of them maybe usedin admixture.

The terminal conversion reaction of polymer A can be carried out byreacting the polymer A obtained after purification with a carboxylategroup-containing compound and a nitrogen atom-containing compound. It isalso possible to carry out the reaction by directly adding a carboxylategroup-containing compound and a nitrogen atom-containing compound to thepolymerization system for producing the polymer A. Thus, it is possibleto omit the step of isolating and purifying the polymer A.

When the polymer A is produced by atom transfer radical polymerizationusing an amine compound or pyridine compound as the ligand, the ligandas it is can be used as the nitrogen atom-containing compound. The aminecompound or pyridine compound is not particularly restricted but thosealready mentioned hereinabove may be used. In this case, too, theconversion reaction can be effected directly in the polymerizationsystem as well. When the conversion reaction is carried out directly inthe polymerization system, a carboxylate-containing compound is addeddirectly to the polymerization system. It produces no problem to add anitrogen atom-containing compound, namely a ligand, to the reactionsystem for accelerating the reaction.

<Polymer>

The polymer obtainable by the production method of the present inventionincludes graft polymers, gels, coupled polymers, terminally functionalpolymers, in particular carboxylic acid group-terminated polymers, andso on.

As specific examples, there may be mentioned vinyl polymers having agroup of the general formula (5) given below within the molecular chainthereof.

R³⁰—[C(O)—O—C(R⁵¹)(R⁵²)—CH₂—A]_(n)  (5)

wherein R⁵¹, R⁵² and R³⁰ are as defined above, n is an integer of notless than 1 and A represents a vinyl polymer.

Specific examples of R³⁰ in the carboxylic acid salts represented by thegeneral formula include all of those mentioned hereinabove.

As the carboxylic acid group-terminated polymer, there may be mentionedvinyl polymers having a terminal structure represented by the followinggeneral formula:

—CH₂—C(R⁵¹)(R⁵²)—O—C(O)—R⁵³—C(O)OH

wherein R⁵¹ and R⁵² are as defined above and R⁵³ represents a directbond or a divalent organic group containing 1 to 20 carbon atoms.

In the above general formula, R⁵³ is a direct bond or a divalent organicgroup containing 1 to 20 carbon atoms. Specific examples of the divalentorganic group containing 1 to 20 carbon atoms are —CH₂—, —(CH₂)₂—,—(CH₂)₃—, —(CH₂)₄—, —(CH₂)_(n)— (n being an integer of 5 to 20) and likealkylene groups. R⁵³ may contain an unsaturated double bond or a benzenering. Further, R⁵³ may contain an ether, ester or amide bond.Furthermore, R⁵³ may be substituted by a functional group such as ahydroxy, amino, nitro or cyano group.

<Curable Composition Comprising the Carboxyl-terminated Polymer as aComponent>

The carboxyl-terminated vinyl polymer produced by the production methodof the present invention can be used in a curable composition comprisingthe same as a component.

This curable composition comprises the following two components asessential components: the carboxyl-terminated vinyl polymer and acompound having two or more functional groups capable of reacting withthe carboxyl group.

The first component carboxyl-terminated (meth)acrylic polymer maycomprise a single species or a mixture of two or more species.

The second component compound having two or more functional groupscapable of reacting with the carboxyl group is not particularlyrestricted but includes, among others, epoxy-containing compounds suchas epoxy resins, hydroxy-containing compounds such as polyfunctionalalcohols, amino-containing compounds such as polyfunctional amines andisocyanato-containing compounds such as polyvalent isocyanate compounds.

The epoxy resins are not particularly restricted but may be any onesknown in the art. Thus, as specific examples, there may be mentionedepoxide resins based on the reaction products from bisphenol A orbisphenol F and epichlorohydrin; di- or polyglycidyl ethers ofpolyhydric aliphatic alcohols such as 1,4-butanediol or of polyalkyleneglycols such as propylene glycol; di- or polyglycidyl ethers ofaliphatic polyols such as 2,2-bis(p-hydroxycyclohexyl)propane; di- orpolyglycidyl ethers of polyhydric phenols such as resorcinol and2,2-bis(4′-hydroxy-3′,5′-dibromophenyl)propane; di- or polyglycidylethers of phenol-formaldehyde condensation products obtainable underacidic conditions, for example phenol novolaks and cresol novolaks;polyglycidyl ethers of polybasic carboxylic acids such as phthalic acid,terephthalic acid, tetrahydrophthalic acid and hexahydrophthalic acid;N-glycidyl derivatives of amines, amides and heterocyclic nitrogenbases, for example N,N-diglycidylaniline, N,N-diglycidyltoluidine,N,N,N′,N′-tetraglycidyl-bis-(p-aminophenyl)methane,triglycidylisocyanurate, N,N′-diglycidylethyleneurea,N,N′-diglycidyl-5,5-dimethylhydantoin andN,N′-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil.

The reaction temperature is not particularly restricted. The reactioncan be carried out at 0° C. to 200° C., preferably at 50° C. to 150° C.For promoting the curing, a catalyst known in the art may be used.Particularly advantageous catalysts are quaternary ammonium compounds orquaternary phosphonium compounds, for example tetramethylammoniumchloride, tetrabutylphosphonium chloride and tetrabutylphosphoniumacetate.

The polyfunctional alcohols are not particularly restricted but, theremay be mentioned, for example, aliphatic glycols such as ethyleneglycol, diethylene glycol, propylene glycol, dipropylene glycol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,neopentyl glycol, 2-ethyl-1,3-hexanediol, glycerol andtrimethylolpropane, alicyclic glycols such as 1,4-cyclohexaneglycol, andaromatic glycols such as xylylene glycol, 1,4-dihydroxyethylbenzene andhydrogenated bisphenol A.

The reaction temperature is not particularly restricted. The reactioncan be carried out at 0° C. to 200° C., preferably at 50° C. to 150° C.

The polyfunctional amines are not particularly restricted but includealiphatic amines such as 1,4-diaminobutane, 1,4-diaminobutane,1,2-diamino-2-methylpropane, 1,5-diaminopentane,2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine, diethylenetriamineand triethylenetetraamine; and aromatic amines such asmetaxylylenediamine, o-, m- or p-phenylenediamine, o-tolidine,m-toluylenediamine, diaminonaphthalane, methylenedianiline anddiaminobenzophenone.

The reaction temperature is not particularly restricted. The reactioncan be carried out at 0° C. to 200° C., preferably at 50° C. to 150° C.

The polyvalent isocyanate compounds are not particularly restricted butinclude those known in the art. Thus, for example, mention may be madeof isocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate, 4,4′-diphenylmethanediisocyanate, hexamethylenediisocyanate, xylylene diisocyanate, metaxylylene diisocyanate,1,5-naphthalenediisocyanate, hydrogenated diphenylmethanediisocyanate,hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate,isophoronediisocyanate and such triisocyanates as Ipposha Yushi's B-45,biuret polyisocyanate compounds such as Sumidur N (product of SumitomoBayer Urethane), isocyanurate ring-containing polyisocyanate compoundssuch as Desmodur IL and HL (product of Bayer A. G.) and Coronate EH(product of Nippon Polyurethane Industry), adduct polyisocyanatecompounds such as Sumidur L (product of Sumitomo Bayer Urethane), adductpolyisocyanate compounds such as Coronate HL (product of NipponPolyurethane Industry) and the like. Blocked polyisocyanates may also beused. These may be used singly or two or more of them may be usedcombinedly.

The reaction temperature is not particularly restricted. The reactioncan be carried out at 0° C. to 200° C., preferably at 50° C. to 150° C.

For promoting the curing reaction between the carboxyl-terminated vinylpolymer and the compound having two or more isocyanate groups, whichconstitute the composition of the present invention, such a knowncatalyst as an organotin compound or a tertiary amine may be added asnecessary. As specific examples of the organotin compound, there may bementioned stannous octoate, dibutyltin diacetate, dibutyltin dilaurate,dibutyltin mercaptides, dibutyltin thiocarboxylates, dibutyltindimaleate and dioctyltin thiocarboxylates, among others. As the tertiaryamine catalyst, there may be mentioned, for example, triethylamine,N,N-dimethylcyclohexylamine, N,N,N′,N′-tetramethyl-ethylenediamine,N,N,N′,N′-tetramethylpropane-1,3-diamine,N,N,N′,N′-tetramethylhexane-1,6-diamine,N,N,N′,N″,N″-pentamethyldiethylenetriamine,N,N,N′,N″,N″-pentamethyldipropylenetriamine, tetramethylguanidine,triethylenediamine, N,N′-dimethylpiperazine, N-methylmorpholine,1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol,N,N,N′-trimethylaminoethylethanolamine,N-methyl-N′-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)morpholine,bis(2-dimethylaminoethyl)ether, ethylene glycolbis(3-dimethyl)aminopropyl ether and the like.

The above two components according to the present invention, whenadmixed with a curing catalyst as necessary and cured, give a uniformcuring product with a high level of core curing.

The polymer produced according to the invention can be utilized as aplastic molding material, plastic shock resistance improving agent,physical property modifier for lubricants, or thermoplastic elastomer,for instance. In case of a functional group-terminated polymer, it canbe converted to a cured product by utilizing the functional group as itis or by converting the functional group to another functional groupsuch as a condensable silyl group and causing the same to undergo acrosslinking reaction. Specific fields of application of the polymerinclude sealing compositions, adhesives, binders, elastic adhesives,coatings, powder coating compositions, foamed products, potting agentsfor use in electric and electronic fields, films, gaskets, variousmoldings and artificial marble, among others.

EXAMPLES

In the following, several specific examples of this invention aredescribed, together with a comparative example. It is to be noted thatthe following examples are by no means limitative of the scope of thepresent invention.

In the following examples, the “number average molecular weight” and“molecular weight distribution (ratio of weight average molecular weightto number average molecular weight)” were determined and calculatedbased on standard polystyrene equivalent values as found by gelpermeation chromatography (GPC). The GPC column used was a column packedwith a crosslinked polystyrene gel and the GPC solvent used waschloroform.

Production Example 1 Synthesis of Br Group-terminated poly(butylacrylate)(1)

A 2-liter separable flask equipped with a reflux condenser and a stirrerwas charged with CuBr (5.54 g, 38.6 mmol) and the reactor inside waspurged with nitrogen. Acetonitrile (73.8 mL) was added and the contentswere stirred on an oil bath at 70° C. for 30 minutes. Thereto were addedbutyl acrylate (132 g), methyl 2-bromopropionate (14.4 mL, 0.129 mol)and pentamethyldiethylenetriamine (4.69 mL, 0.022 mol) to therebyinitiate the reaction. While heating at 70° C. with stirring, butylacrylate (528 g) was added dropwise continuously over 90 minutes,followed by further 80 minutes of heating with stirring.

The reaction mixture was diluted with toluene and passed through anactivated alumina column. The volatile matter was then distilled offunder reduced pressure to give poly(butyl acrylate) having a Br group atone terminus (polymer [1]). The polymer [1] had a number averagemolecular weight of 5,800 and a molecular weight distribution of 1.14.

Production Example 2 Synthesis of a polycarboxylic Acid Salt

tert-Butoxypotassium (7.68 g, 68.4 mmol) was dissolved in methanol (100mL) and then adipic acid (5.0 g, 34.2 mmol) was added to the solution.After stirring the reaction mixture at room temperature for a while, themixture was concentrated and the residue dried to give dipotassiumadipate.

Example 1 Introduction of a Carboxylic Acid Salt Group

A flask equipped with a reflux condenser was charged with the polymer[1] obtained in Production Example 1, an excess of the dipotassiumadipate obtained in Production Example 2 and dimethylacetamide, and thecontents were heated at 100° C. for at least 10 hours with stirring. Thereaction mixture was concentrated under reduced pressure and theconcentrate was diluted with toluene. The insoluble matter was filteredoff and the filtrate was concentrated under reduced pressure to give apolymer.

As a result of ¹H NMR analysis and GPC measurement, it was found thatthe terminal Br group of polymer [1] had been converted and thecarboxylic acid salt group had been introduced into the polymerterminus.

Example 2 Coupling of the Br Group-terminated Polymer

A-500 mL flask equipped with a reflux condenser was charged with thepolymer [1] (10 g) obtained in Production Example 1, the dipotassiumadipate (191 mg) obtained in Production Example 2 and dimethylacetamide(10 mL), and the contents were heated at 70° C. for 5 hours withstirring. The dipotassium adipate (540 mg) was further added and themixture was heated at 100° C. for further 10 hours with stirring. Thereaction mixture was concentrated under reduced pressure, and theconcentrate was diluted with toluene. The insoluble matter was filteredoff and the filtrate was concentrated under reduced pressure to give apolymer. Conversion of the Br group was confirmed by ¹H NMR analysis andformation of a macromolecular product (peak top molecular weight=12,500)was confirmed by GPC measurement. These findings indicated mutualcoupling of terminal Br groups.

Example 3 Synthesis of a Graft Copolymer

The polymer [1] (5 g) obtained in Production Example 1 and poly(sodiumacrylate) (5 g, product of Wako Pure Chemical Industries) were mixed upand heated at 150° C. for 1 hour. The unreacted polymer [1] fraction wasextracted with acetone to give a graft copolymer. The graft copolymerwas insoluble in acetone but well dispersible in water.

Production Example 3 Synthesis of an Alkenyl-containing Carboxylic AcidSalt

Undecylenic acid (18.8 g, 0.102 mol) was added dropwise gradually to ½ Nethanolic solution of potassium hydroxide (200 mL) with stirring at 0°C. The volatile matter was distilled off under reduced pressure to givea crude product. The crude product was washed with acetone and heatedunder reduced pressure to give potassium undecylenate represented by theformula given below as a white solid (8.88 g, yield 88%).CH₂═CH—(CH₂)₈—CO₂ ⁻K⁺

Production Example 4 Synthesis of Br-terminated poly(butyl acrylate) (2)

A 100-mL glass reactor was charged with butyl acrylate (20.0 mL, 17.9 g,0.140 mol), CuBr (0.625 g, 4.36 mmol), pentamethyldiethylenetriamine(0.91 mL, 0.755 g, 4.36 mmol) and acetonitrile (5 mL) and, aftercooling, deaerated under reduced pressure and then nitrogen gas wasintroduced thereinto. After thorough stirring, methyl 2-bromopropionate(0.973 mL, 1.456 g, 8.72 mmol) was added. While heating at 70° C. withstirring, 30 mL of butyl acrylate was added dropwise slowly and thereaction was allowed to proceed. The mixture was treated with activatedalumina and then the volatile matter was distilled off by heating underreduced pressure. The product was dissolved in ethyl acetate and washedwith 2% hydrochloric acid and then with brine. The organic layer wasdried over Na₂SO₄ and the volatile matter was distilled off by heatingunder reduced pressure to give a halogen-terminated polymer (polymer[2]). The polymer had a number average molecular weight of 5,270 and amolecular weight distribution of 1.08.

Example 4 Acceleration of the Substitution Reaction by Addition of anAmine (1)

The polymer [2] (1.5 g) obtained in Production Example 4, the potassiumundecylenate (615 mg, 0.277 mmol) obtained in Production Example 3,triethylamine (12.7 mg, 0.126 mmol) and acetonitrile (0.84 mL) werecharged, and the mixture was heated at 70° C. for 12 hours withstirring. Ethyl acetate was added to the mixture, the insoluble matterwas filtered off, and the filtrate was washed with water. The organiclayer was concentrated to give a polymer. The terminal bromineconversion was 49%.

Example 5 Acceleration of the Substitution Reaction by Addition of anAmine (2)

The procedure of Example 4 was followed in the same manner except thattetramethylethylenediamine (14.5 mg, 0.125 mmol) was used in lieu oftriethylamine. The polymer obtained showed a terminal bromine conversionof 58%.

Comparative Example 1 Comparison with the Acceleration of theSubstitution Reaction by Addition of an Amine

For comparison, the reaction was carried out without using any nitrogenatom-containing compound. The procedure of Example 4 was followedwithout using the amine. The polymer obtained showed a terminal bromineconversion of 15%.

Production Example 5 Reaction of a Functional Group-containing Alcoholwith a Cyclic Acid Anhydride

A 100-mL three-necked round-bottom flask was fitted with a refluxcondenser and, in a nitrogen atmosphere, the flask was charged withphthalic anhydride (4.0 g, 13.5 mmol) and allyl alcohol (4.58 mL), andthe contents were stirred at 90° C. for 30 minutes. The unreacted allylalcohol fraction was distilled off under reduced pressure to givephthalic acid monoallyl ester (yield 5.66 g).

Potassium methoxide (1.70 g) was dissolved in methanol (20 mL) and theabove carboxylic acid (5.00 g) was added, and the mixture was stirredthoroughly at room temperature. The volatile matter was distilled offunder reduced pressure to give the potassium salt of the carboxylicacid.

Example 6 Polymer Terminal Br Conversion Using a Carboxylic Acid SaltObtained by Reaction of a Functional Group-containing Alcohol with aCyclic Acid Anhydride

Using CuBr (0.625 g) as the catalyst, pentamethyldiethylenetriamine(0.83 mL) as the ligand and diethyl 2,5-dibromoadipate (1.57 g) as theinitiator, butyl acrylate was polymerized at 70° C. to give poly(butylacrylate) having bromine at both ends with a number average molecularweight of 10,900 and a molecular weight distribution of 1.12.

Then, the above polymer (8.1 g), the carboxylic acid potassium salt(0.333 g) obtained in Production Example 5, and dimethylacetamide (16.2mL) were charged, and the reaction was allowed to proceed at 70° C. in anitrogen atmosphere for 0.5 hour. Ethyl acetate was added to the mixtureand the whole mixture was washed with water. The organic layer wasconcentrated to give a polymer. The number of alkenyl groups introducedper polymer molecule was found to be 1.44 by ¹H NMR analysis.

INDUSTRIAL APPLICABILITY

By substituting a polymer terminus with a carboxylic acid salt accordingto the invention, it is possible to effect, in a simple and easy manner,the coupling of a polymer derived from a radical-polymerizable monomerwhich is difficult to attain by the prior art technology. According tothe invention, it is also possible to produce functionalgroup-terminated vinyl polymers in a simple and easy manner. Similarly,it is also possible to produce, in a simple and easy manner, graftcopolymers having a vinyl polymer as a branch polymer from ahalogen-terminated vinyl polymer and a polymer having a side-chaincarboxylate group through conversion of the terminal halogen atom(s) toa carboxylate group(s). Further, those vinyl polymers having a highproportion of carboxyl group(s) at a main chain terminus thereof whichhave been difficult to produce in the prior art can be produced in asimple and easy manner. Curable compositions comprising such polymersgive cured products having very satisfactory characteristics, such asgood rubber elasticity.

Furthermore, by utilizing cyclic carboxylic acid anhydrides, it becomespossible to obtain, in a simple and easy manner, vinyl polymers having ahigh proportion of a functional group at a main chain terminus thereof.By carrying out the reaction according to the invention in the presenceof a nitrogen atom-containing compound, it is possible to accelerate theconversion reaction. It is further possible to carry out the conversionreaction directly in the polymerization system for vinyl polymerproduction.

What is claimed is:
 1. A method of producing a polymer which comprisessubstitution of carboxylic acid group for a terminal halogen group of apolymer obtained by atom transfer radical polymerization, saidsubstitution of carboxylic acid group comprising using a carboxylic acidgroup-containing compound, and said carboxylic acid group-containingcompound being a polymer.
 2. The method of producing a polymer accordingto claim 1, wherein the carboxylic acid group is a carboxylic acid saltgroup.
 3. The method of producing a polymer according to claim 2,wherein the carboxylic acid salt group is a carboxylic acid potassiumsalt group.
 4. The method of producing a polymer according to claim 1,wherein the atom transfer radical polymerization is carried out using atransition metal complex as the polymerization catalyst, said transitionmetal complex being a transition metal complex whose central metal is anelement of the group 7, 8, 9, 10 or 11 of the periodic table of theelements.
 5. The method of producing a polymer according to claim 4,wherein the transition metal complex is a complex of copper, nickel,ruthenium or iron.
 6. The method of producing a polymer according toclaim 5, wherein the transition metal complex is a copper complex. 7.The method of producing a polymer according to claim 1, wherein thepolymer obtained by atom transfer radical polymerization is obtained bypolymerization of a (meth)acrylic monomer.
 8. The method of producing apolymer according to claim 7, wherein the (meth)acrylic monomer is anacrylic ester monomer.
 9. The method of producing a polymer according toclaim 1, wherein the terminal halogen group of the polymer obtained byatom transfer radical polymerization is a secondary halogen group. 10.The method of producing a polymer according to claim 1, wherein thepolymerization is carried out in the presence of a nitrogenatom-containing compound.
 11. The method of producing a polymeraccording to claim 10, wherein the nitrogen atom-containing compound isselected from the group consisting of aliphatic amines, alicyclicamines, aromatic amines and heterocyclic nitrogen bases.
 12. The methodof producing a polymer according to claim 10, wherein the atom transferradical polymerization is carried out using an amine compound orpyridine compound as a ligand to the catalyst and using said ligand alsoas the nitrogen atom-containing compound.
 13. The method of producing apolymer according to claim 12, wherein the atom transfer radicalpolymerization is for polymerizing a vinyl monomer and the carboxylicacid group substitution reaction is effected by adding acarboxyl-containing compound directly to the polymerization system. 14.The method of producing a polymer according to claim 1, wherein thecarboxylic acid group-containing compound has a carboxylic acid group ina side chain thereof.
 15. The method of producing a polymer according toclaim 14, wherein a polymer obtained by the substitution reaction is agraft polymer.
 16. The method of producing a polymer according to claim14, wherein a polymer obtained by the substitution reaction is a gel.17. A method of producing a polymer which comprises substitution ofcarboxylic acid group for a terminal halogen group of a polymer obtainedby atom transfer radical polymerization, said substitution of carboxylicacid group comprising using a carboxylic acid group-containing compound,and said carboxylic acid group-containing compound having two or morecarboxylic acid groups.
 18. The method of producing a polymer accordingto claim 17, wherein the carboxylic acid group is a carboxylic acid saltgroup.
 19. The method of producing a polymer according to claim 18,wherein the carboxylic acid salt group is a carboxylic acid potassiumsalt group.
 20. The method of producing a polymer according to claim 17,wherein the atom transfer radical polymerization is carried out using atransition metal complex as the polymerization catalyst, said transitionmetal complex being a transition metal complex whose central metal is anelement of the group 7, 8, 9, 10 or 11 of the periodic table of theelements.
 21. The method of producing a polymer according to claim 20,wherein the transition metal complex is a complex of copper, nickel,ruthenium or iron.
 22. The method of producing a polymer according toclaim 21, wherein the transition metal complex is a copper complex. 23.The method of producing a polymer according to claim 17, wherein thepolymer obtained by atom transfer radical polymerization is obtained bypolymerization of a (meth)acrylic monomer.
 24. The method of producing apolymer according to claim 23, wherein the (meth)acrylic monomer is anacrylic ester monomer.
 25. The method of producing a polymer accordingto claim 18, wherein the terminal halogen group of the polymer obtainedby atom transfer radical polymerization is a secondary halogen group.26. The method of producing a polymer according to claim 18, wherein thepolymerization is carried out in the presence of a nitrogenatom-containing compound.
 27. The method of producing a polymeraccording to claim 26, wherein the nitrogen atom-containing compound isselected from the group consisting of aliphatic amines, alicyclicamines, aromatic amines and heterocyclic nitrogen bases.
 28. The methodof producing a polymer according to claim 26, wherein the atom transferradical polymerization is carried out using an amine compound orpyridine compound as a ligand to the catalyst and using said ligand alsoas the nitrogen atom-containing compound.
 29. The method of producing apolymer according to claim 28, wherein the atom transfer radicalpolymerization is for polymerizing a vinyl monomer and the carboxylicacid group substitution reaction is effected by adding acarboxyl-containing compound directly to the polymerization system. 30.The method of producing a polymer according to claim 17, whereinsubstitution reaction is effected with a compound having two or morecarboxylic acid groups, whereby the carboxylic acid groups areintroduced into termini of the resulting polymer.
 31. The method ofproducing a polymer according to claim 17, wherein substitution reactionis effected with a compound having two or more carboxylic acid groups,whereby polymer molecules are coupled together.
 32. A method ofproducing a polymer which comprises substitution of carboxylic acidgroup for a terminal halogen group of a polymer obtained by atomtransfer radical polymerization, said substitution of carboxylic acidgroup comprising using a carboxylic acid group-containing compound, andsaid carboxylic acid group-containing compound being obtained byreacting a cyclic acid anhydride with a functional group-containingalcohol.
 33. The method of producing a polymer according to claim 32,wherein the carboxylic acid group is a carboxylic acid salt group. 34.The method of producing a polymer according to claim 33, wherein thecarboxylic acid salt group is a carboxylic acid potassium salt group.35. The method of producing a polymer according to claim 32, wherein theatom transfer radical polymerization is carried out using a transitionmetal complex as the polymerization catalyst, said transition metalcomplex being a transition metal complex whose central metal is anelement of the group 7, 8, 9, 10 or 11 of the periodic table of theelements.
 36. The method of producing a polymer according to claim 35,wherein the transition metal complex is a complex of copper, nickel,ruthenium or iron.
 37. The method of producing a polymer according toclaim 36, wherein the transition metal complex is a copper complex. 38.The method of producing a polymer according to claim 32, wherein thepolymer obtained by atom transfer radical polymerization is obtained bypolymerization of a (meth)acrylic monomer.
 39. The method of producing apolymer according to claim 38, wherein the (meth)acrylic monomer is anacrylic ester monomer.
 40. The method of producing a polymer accordingto claim 32, wherein the terminal halogen group of the polymer obtainedby atom transfer radical polymerization is a secondary halogen group.41. The method of producing a polymer according to claim 32, wherein thepolymerization is carried out in the presence of a nitrogenatom-containing compound.
 42. The method of producing a polymeraccording to claim 41, wherein the nitrogen atom-containing compound isselected from the group consisting of aliphatic amines, alicyclicamines, aromatic amines and heterocyclic nitrogen bases.
 43. The methodof producing a polymer according to claim 41, wherein the atom transferradical polymerization is carried out using an amine compound orpyridine compound as a ligand to the catalyst and using said ligand alsoas the nitrogen atom-containing compound.
 44. The method of producing apolymer according to claim 43, wherein the atom transfer radicalpolymerization is for polymerizing a vinyl monomer and the carboxylicacid group substitution reaction is effected by adding acarboxyl-containing compound directly to the polymerization system. 45.The method of producing a polymer according to claim 32, wherein thefunctional group is selected from the group consisting of alkenyl,hydroxyl, amino and epoxy groups.
 46. The method of producing a polymeraccording to claim 32, wherein the cyclic acid anhydride is selectedfrom the group consisting of succinic anhydride, phthalic anhydride andglutaric anhydride.
 47. The method of producing a polymer according toclaim 46, wherein the cyclic acid anhydride is phthalic anhydride.